Method of and apparatus for manufacturing methanol

ABSTRACT

In a method of and apparatus for manufacturing methanol and higher alcohols from natural gas a catalytic area is formed on the exterior of a gas permeable partition. Natural gas is maintained on the interior of the gas permeable partition at predetermined pressure. Relative movement between the gas permeable partition and the water forms sub-micron sized bubbles of natural gas. Electromagnetic radiation is directed onto the catalytic surface to form hydroxyl radicals from the water. Methyl, ethyl, and propyl ions from the natural gas combine with the hydroxyl ions to form methanol, ethanol, and propanol.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of prior application Ser. No.09/368,404 filed Aug. 4, 1999, currently pending which is acontinuation-in-part of prior application Ser. No. 09/224,394 filed Dec.31, 1998, now U.S. Pat. No. 6,129,818 which is a continuation-in-part ofprior application Ser. No. 09/058,494, filed Apr. 10, 1998, now U.S.Pat. No. 5,954,925.

TECHNICAL FIELD

This invention relates generally to the manufacture of methanol, andmore particularly to a method of and apparatus for manufacturingmethanol from methane, and to a method of and apparatus formanufacturing methanol, ethanol, and propanol from natural gas.

BACKGROUND AND SUMMARY OF THE INVENTION

Methanol, the simplest of the alcohols, is a highly desirable substancewhich is useful as a fuel, as a solvent, and as a feedstock in themanufacturer of more complex hydrocarbons. In accordance with the methodof methanol manufacture that is currently practiced in the petroleumindustry, methane is first converted to synthesis gas, a mixture ofcarbon monoxide and hydrogen. The synthesis gas is then converted overan alumina-based catalyst to methanol. The formation of synthesis gasfrom methane is an expensive process.

Although often identified as methane, the feedstock for the foregoingsynthesis gas process is typically natural gas. As is well known,natural gas often contains significant percentages of sulphur. Sincesulphur poisons the catalyst required for its operation, the synthesisgas process for making methanol is further limited by the scarcity oflow sulphur natural gas.

As will be apparent, methane and methanol are closely relatedchemically. Methane comprises a major component of natural gas and istherefore readily available. Despite the advantages inherent inproducing methanol directly from methane, no commercially viable systemfor doing so has heretofore been developed.

The present invention comprises a method of and apparatus formanufacturing methanol from methane or natural gas which overcomes theforegoing and other deficiencies which have long since characterized theprior art. The method involves a gas permeable partition upon which alight-activated catalyst capable of producing hydroxyl radicals fromwater is deposited, it being understood that as used herein the term“light-activated catalyst” means any catalyst that is activated byelectromagnetic radiation regardless of wave length.

Water is present on the catalyst side of the partition and methane ornatural gas at positive pressure is present on the opposite side of thepartition. The catalyst is exposed to radiation while relative movementis effected between the water and the partition. The radiation-exposedcatalyst reacts with the water molecules to form hydroxyl radicals. Thegas is forced through the semipermeable partition forming small bubblesin the water. The hydroxyl radicals in the water then undergo afree-radical reaction with the methane in the water to form methanol,and if natural gas is used in the process, ethanol and propanol.

In accordance with the broader aspects of the invention there isgenerated a stream of sub-micron sized gas bubbles. Due to theirextremely small size, the gas bubbles present an extremely large surfacearea which increases reaction efficiency. Smaller pores in the gaspermeable partition facilitate the formation of smaller bubbles.Additionally, higher relative velocity across the partition surface aidsin shearing the bubbles off the surface while they are still small.

In accordance with first, second, and third embodiments of theinvention, a gas permeable tube has an exterior coating comprising atitanium-based catalyst. The gas permeable tube is positioned within aglass tube and water is caused to continuously flow through the annularspace between the two tubes. Methane or natural gas is directed into theinterior of the gas permeable tube and is maintained at a pressure highenough to cause gas to pass into the water and prevent the flow of waterinto the interior of the gas permeable tube. As the water passes overthe gas permeable tube, gas bubbles are continually sheared off of itssurface. The gas bubbles thus generated are sub-micron in size andtherefore present an extremely large surface area.

Electromagnetic radiation generated, for example, by ultraviolet lampsis directed through the glass tube and engages the titanium-basedcatalyst to generate hydroxyl radicals in the flowing water. Thehydroxyl radicals undergo a free-radical reaction with the methaneforming methanol, among other free-radical reaction products.Subsequently, the methanol and other products are separated from thereaction mixture by distillation.

In accordance with fourth, fifth, sixth, seventh, and eighth embodimentsof the invention, there is provided a hollow disk which supports a gaspermeable partition having an exterior coating comprising atitanium-based catalyst. The disk is positioned within a water filledcontainer. Methane or natural gas is directed into the interior of thedisk and is maintained at a pressure high enough to cause gas to passoutwardly through the partition and into the water and to prevent theflow of water into the interior of the disk. The disk and the partitionare moved at high speed relative to the water. As the gas permeablepartition moves relative to the water, gas bubbles are continuallysheared off of its surface. The gas bubbles thus generated aresub-micron in size and then therefore present an extremely large surfacearea.

Electromagnetic radiation generated, for example, by ultraviolet lampswithin the container engages the titanium-based catalyst to generatehydroxyl radicals in the water. The hydroxyl radicals undergo afree-radical reaction with the methane forming methanol, and, if naturalgas is used in the process, ethanol and propanol. Subsequently, themethanol and other reaction products are separated from the reactionmixture by distillation.

In the practice of the fifth, sixth, seventh, and eighth embodiments ofthe invention, utilization of the energy comprising the electromagneticradiation is maximized by providing a mirror within the hollow disk toreflect electromagnetic radiation passing through the porous partitionback to the catalytic material. The mirror may comprise either amirrored surface of the hollow disk or a separate mirror plate.Fluorescent material is utilized to convert broad-band electromagneticradiation to radiation having a band width which is specific to theselected catalyst. The fluorescent material may be combined with theporous partition, or with the catalytic layer, or may comprise adistinct layer.

In accordance with a ninth embodiment of the invention, a plurality ofparallel porous partitions each having a photocatalytic layer on itsexterior surface are mounted in an array. The array further comprisessources of electromagnetic radiation positioned between each of thetubular porous partition/photocatalytic layer assemblies. Methane ornatural gas from a first manifold is directed into the interior of eachof the parallel porous partitions. Water from a second manifold isdirected across the surface of the photocatalytic layers in the mannerof the first three embodiments of the invention. In addition toactivating the photocatalytic layers, energy from the electromagneticradiation sources generally provides sufficient heat to distill theresulting methanol and higher alcohols from the water.

In accordance with a tenth embodiment of the invention, an oxidizer suchas oxygen, peroxide, etc. is mixed with methane or natural gas. Themixture is then directed through a porous partition having aphotocatalytic layer on its exterior surface. Water is continuouslydirected across the exterior surface of the porous partition in themanner of the first nine embodiments of the invention. In this mannerthe reaction is rendered self-sustaining.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete understanding of the invention may be had by referenceto the following Detailed Description when taken in conjunction with theaccompanying Drawings wherein:

FIG. 1 is a diagrammatic illustration of a method and apparatus formanufacturing methanol comprising a first embodiment of the presentinvention.

FIG. 2 is a diagrammatic illustration of a second embodiment of theapparatus of the present invention with a rotating sintered stainlesssteel tube.

FIG. 3 is a diagrammatic illustration of a third embodiment of theapparatus of the present invention with a rotating sintered stainlesssteel tube with turbines.

FIG. 4 is a diagrammatic illustration of a fourth embodiment of theapparatus of the present invention.

FIG. 5 is an enlargement of a portion of FIG. 4.

FIG. 6 is an illustration similar to FIG. 5 showing an alternativeconstruction useful in the practice of the invention.

FIG. 7 is an exploded view of a modification of the hollow disk of FIG.4 comprising a fifth embodiment of the invention.

FIG. 8 is an assembly view of the fifth embodiment of the invention.

FIG. 9 is an exploded view of a modification of the hollow disk of FIG.4 comprising a sixth embodiment of the invention.

FIG. 10 is an assembly view of the sixth embodiment of the invention.

FIG. 11 is an exploded view of a modification of the hollow disk of FIG.4 comprising a seventh embodiment of the invention.

FIG. 12 is an assembly view of the seventh embodiment of the invention.

FIG. 13 is an exploded view of a modification of the hollow disk of FIG.4 comprising an eighth embodiment of the invention.

FIG. 14 is an assembly view of the eighth embodiment of the invention.

FIG. 15 is a diagrammatic illustration of a ninth embodiment of theinvention.

FIG. 16 is a flow chart illustrating a tenth embodiment of theinvention.

DETAILED DESCRIPTION

Referring now to the Drawings, and particularly to FIG. 1 thereof, thereis shown an apparatus for manufacturing methanol 10 comprising a firstembodiment of the invention. The apparatus 10 includes a gas permeabletube 12 positioned within a glass tube 14. The tube 12 can comprisesintered stainless steel, or sintered glass, sintered ceramic materials,or a photocatalytic material. As illustrated in FIG. 1, both the gaspermeable tube 12 and the glass tube 14 comprise right circularcylinders with the tube 12 extending concentrically relative to the tube14. Other geometrical configurations of and positional relationshipsbetween the gas permeable tube 12 and the glass tube 14 may be utilizedin accordance with the requirements of particular applications of theinvention.

If not formed from a photocatalytic materiel, the gas permeable tube 12has a light-activated catalyst layer 16 formed on the exterior surfacethereof. The catalyst layer 16 is preferably a titanium-based catalyst;however, it will be understood that any light-activated catalyst whichforms hydroxyl radicals from water may be utilized in the practice ofthe invention, if desired. A plurality of electromagnetic radiationsources 18, such as ultraviolet lamps, are positioned around theexterior of the glass tube 14, it being understood that while only onesource 18 is illustrated in FIG. 1, in actual practice a plurality ofenergy sources 18 are employed and are disposed around the entireperiphery of the tube 14. As illustrated by the waves 20 in FIG. 1, thesources 18 generate energy in the form of, for example, ultravioletlight which is directed through the glass tube 14 and onto the catalyticlayer 16 formed on the exterior surface of the gas permeable tube 12.

In the operation of the apparatus for manufacturing methanol 10, aquantity of water is received in a reservoir 22. Water from thereservoir 22 is directed into the annular space between the gaspermeable tube 12 and the glass tube 14 through piping 24. During theoperation of the apparatus 10 water flows through the annulus betweenthe gas permeable tube 12 and the glass tube 14 on a continuous basis.

A quantity of methane or natural gas is stored in a reservoir 26. In theoperation of the apparatus 10, gas is directed from the reservoir 26into the interior of the gas permeable tube 12 through piping 28. Thegas within the gas permeable tube 12 is maintained at a pressure highenough to cause the gas to pass through the walls of the tube 12 intothe water and to prevent the flow of water into the interior of the tube12.

In the operation of the apparatus for manufacturing methanol 10, thewater flowing through the annular space between the gas permeable tube12 and the glass tube 14 causes gas bubbles to be continuously strippedoff the exterior surface of the tube 12. In this manner the size of thegas bubbles is maintained in the sub-micron range. The sub-micron sizeof the gas bubbles provides an enormous methane surface area which inturn results in unprecedented reaction efficiency.

As the sub-micron size gas bubbles are produced by the flow of waterover the exterior surface of the gas permeable tube 12, energy from thesources 18 continuously engages the catalytic surface 16 formed on theexterior of the tube 12. This generates hydroxyl radicals in the flowingwater. It is theorized that the hydroxyl radicals homolyticaly cleaveone or more of the carbon-hydrogen bonds in the methane thereby formingeither molecules of hydrogen or molecules of water, depending upon theinitiating radical, and methyl radicals. The methyl radicals combineeither with the hydroxyl radicals to form methanol or with the hydrogenradicals to form methane.

Those skilled in the art will appreciate the fact that other chemicalreactions are possible in the operation of the apparatus formanufacturing methanol 10. For example there exists the possibility of amethyl-methyl radical reaction, and also the possibility of ahydrogen-hydrogen radical reaction. Both of these possibilities areextremely remote due to the relatively low concentrations of methylradicals and hydrogen radicals at any given time.

It will be further understood that natural gas typically comprises up to10% ethane and up to 2% propane in addition to methane. Therefore, ifnatural gas is used in the practice of the invention, the reactionproducts include ethanol, normal propanol, and isopropanol in additionto methanol.

The water flowing from the annulus between the gas permeable tube 12 andthe glass tube 14 having the reaction products contained therein isdirected to a distillation apparatus 30 through piping 32. Thedistillation apparatus 30 separates the outflow from the space betweenthe tube 12 and the tube 14 into at least four streams, including astream of unreacted methane 34 which is returned to the reservoir 26, astream of water 36 which is returned to the reservoir 22, a stream ofother reaction products 38 which are recovered, and a stream of methanol40. The stream of other reaction products 38 may be further separatedinto its component parts, if desired.

The present invention further comprises a method of making methanol. Inaccordance with the method there is provided a continuously flowingstream of water. Sub-micron size bubbles of methane are continuouslyinjected into the flowing water. Hydroxyl radicals are continuouslygenerated from the water. It is theorized that the hydroxyl radicalscleave the hydrogen-carbon bonds of the methane to form methyl radicals.The methyl radicals combine with the hydroxyl radicals to form methanol.

In accordance with more specific aspects of the method, a gas permeabletube having a catalytic layer on the exterior surface thereof ispositioned within a glass tube. Water is directed through the annulusbetween the gas permeable tube and the glass tube, and methane ornatural gas is directed into the interior of the gas permeable tube. Thewater flowing between the gas permeable tube and the glass tubecontinuously strips sub-micron size bubbles from the exterior surface ofthe gas permeable tube.

Electromagnetic radiation from, for example, ultraviolet lamps isdirected through the glass tube and engages the catalytic surface on theexterior of the gas permeable tube, thereby forming hydroxyl radicalsfrom the flowing water. It is theorized that the hydroxyl radicalshomolyticaly cleave one or more of the carbon-hydrogen bonds in themethane to form either molecules of hydrogen or molecules of water, andmethyl radicals. The methyl radicals combine either with the hydroxylradicals to form methanol or with the hydrogen radicals to form methane.Ethanol and propanol are also produced if natural gas is used in theprocess.

The use of an internal gas permeable partition cylinder is shown in FIG.1. One skilled in the art would also recognize that a vast number ofshapes and orientations could be used to accomplish the same purpose.For example, the glass tube 14 does not need to be shaped as a tube inorder to be functional as a housing. In fact, such a housing need onlybe partially transparent to electromagnetic radiation for the apparatusto function. Additionally, the orientation of the gas inside an innertube with water between the inner tube and a housing is not required.One skilled in the art could envision a housing bisected by a gaspermeable partition creating a water chamber and a gas chamber. The onlyrequirements of such an embodiment is that the water chamber has a watersource and a product outlet, which leads to an isolation apparatus,preferably a distillation apparatus; the gas chamber has a gas source;the gas permeable partition has a catalytic layer that is exposed toelectromagnetic energy on the water side of the partition; and the gaspermeable partition allows the penetration of gas bubbles that aresheared off by the relative movement of water in the water chamberrelative to the gas permeable membrane.

Referring now to FIG. 2, there is shown an apparatus for manufacturingmethanol comprising a second embodiment of the invention. The apparatus50 comprises numerous component parts which are substantially identicalin construction and function to the apparatus for manufacturing methanol10 shown in FIG. 1 and described hereinabove in conjunction therewith.Such identical component parts are designated in FIG. 2 with the samereference numerals utilized in the description of the apparatus 10, butare differentiated therefrom by means of a prime (′) designation.

In the apparatus for manufacturing methanol 50, the gas permeable tube12′ is supported for rotation relative to the glass tube 14′ by sealedbearings 52. Those skilled in the art will appreciate the fact thatbearing/seal assemblies comprising separate components may be utilizedin the practice of the invention, if desired.

A motor 54 is mounted at one end of the glass tube 14′ and isoperatively connected to the gas permeable tube 12′ to effect rotationthereof relative to the glass tube 14′. The glass tube 14′ includes anend portion 56 which is isolated from the remainder thereof by a seal58. The portion of the tube 12′ extending into the end portion 56 of theglass tube 14′ is provided with a plurality of uniform or nonuniformapertures 60.

In the operation of the apparatus for manufacturing methanol 50, methaneor natural gas is directed from the reservoir 26′ through the piping28′, through the end portion 56 of the glass tube 14′ and through theapertures 60 into the interior of the gas permeable tube 12′. Waterflows from the reservoir 22′ through the piping 24′ and into the portionof the glass tube 14′ that is isolated from the end portion 56 by theseal 58. Water flows out of the glass tube 14′ through piping 32′ to thedistillation apparatus 30′.

The operation of the apparatus for manufacturing methanol 50 of FIG. 2differs from the operation of the apparatus for manufacturing methanol10 of FIG. 1 in that in the operation of the apparatus 50, the relativemovement between the bubbles forming on the surface of the gas permeabletube 12′ and the water contained within the glass tube 14′ is controlledby the motor 54 rather than the flow rate of the water as it passesthrough the glass tube 14′. This is advantageous in that it allows thegas permeable tube 12′ to be rotated at a relatively high velocityrelative to the water contained within the glass tube 14′, therebyassuring that sub-micron size bubbles will be sheared from the surfaceof the gas permeable tube 12′. Meanwhile, the velocity of the waterpassing through the interior of the glass tube 12′ can be relativelyslow, thereby assuring a maximum number of sub-micron size bubblesentering the water per unit volume thereof.

An apparatus for manufacturing methanol comprising a third embodiment ofthe invention is illustrated in FIG. 3. The apparatus for manufacturingmethanol 60 comprises numerous component parts which are substantiallyidentical in construction and function to component parts of theapparatus for manufacturing methanol 10 illustrated in FIG. 1 anddescribed hereinabove in conjunction therewith. Such identical componentparts are designated in FIG. 3 with the same reference numerals utilizedin the description of the apparatus 10, but are differentiated therefromby means of a double prime (41 ) designation.

The apparatus for manufacturing methanol 60 comprises a gas permeabletube 12″ which is supported for rotation relative to the glass tube 14″by sealed bearings 62. Those skilled in the art will appreciate the factthat the apparatus 60 may be provided with bearing/seal assembliescomprising separate components, if desired.

The gas permeable tube 12″ is provided with one or more turbines 64. Thepitch of the turbines 64 is adjusted to cause the tube 12″ to rotate ata predetermined speed in response to a predetermined flow rate of waterthrough the glass tube 14″.

Similarly to the apparatus for manufacturing methanol of FIG. 2, the useof the apparatus for manufacturing methanol 60 is advantageous in thatthe gas permeable tube 12″ can be caused to rotate relatively rapidly inresponse to a relatively low flow rate of water through the glass tube14″. This assures that sub-micron size bubbles will be stripped from theouter surface of the gas permeable tube 12″ and that a maximum number ofbubbles will be received in the water flowing through the glass tube 14″per unit volume thereof. The use of the apparatus for manufacturingmethanol 60 is particularly advantageous in applications of theinvention wherein water flows through the system under the action ofgravity, in that the use of the turbines 64 eliminates the need for aseparate power source to effect rotation of the gas permeable tube 12″relative to the glass tube 14″.

Referring now to FIGS. 4 and 5, there is shown a method of and apparatusfor manufacturing methanol and other alcohols 70 comprising a fourthembodiment of the invention. In accordance with a fourth embodiment ofthe invention, there is provided a distillation unit 72 comprising atank having a quantity of water 74 contained therein. One or moreelectromagnetic radiation sources 76 are also positioned in the tank 72.The distillation unit 72 includes a heat source, which may comprise theradiation sources 76, sufficient to effect distillation of methanol andother alcohols from water.

A hollow disk 78 is mounted in the lower portion of the tank 78. As isbest shown in FIG. 5, the disk 78 includes a gas permeable partition 80supported on a tube 82 for rotation within the tank 72 under theoperation of a motor 84. The partition 80 may comprise sinteredstainless steel, sintered glass, or sintered ceramic materials, or maybe formed entirely from a catalytic material, depending upon therequirements of particular applications of the invention. Natural gasreceived from a supply 86 is directed through piping 88 and a suitablecommutator 90 into the tube 82 and through the tube 82 into the interiorof the hollow disk 78. The tube 82 has a hollow interior 90 and the disk78 has a hollow interior 92 connected in fluid communication therewith.The gas permeable partition 80 is coated with a light-activatedcatalytic layer 94.

The disk 78 is supplied with natural gas at a pressure just high enoughto overcome to head pressure of the water 74. The disk 78 is rotated bythe motor 84 at an appropriate speed in contact with the water 74 suchthat a shearing phenomenon occurs at the surface of the photocatalyticlayer 94 thus producing bubbles of natural gas of extremely small size.The extreme small size of the bubbles thus produced results in a surfacearea to volume ratio of small bubbles which significantly improves theefficiency of the reaction.

As the sub-micron size gas bubbles are produced by movement of theexterior surface of the gas permeable partition 80 in the water 74,electromagnetic energy from the sources 76 continuously engages thecatalytic surface 94 formed on the exterior of the partition 80, itbeing understood that depending on the characteristics of the catalyticlayer 94, energy comprising various portions of the electromagneticspectrum may be used in the practice of the invention.

Activation of the catalytic layer 94 generates hydroxyl radicals in thewater. It is theorized that the hydroxyl radicals homolyticaly cleaveone or more of the carbon-hydrogen bonds in the methane, ethane,propane, etc., thereby forming either molecules of hydrogen or moleculesof water, depending upon the initiating radical, and methyl, ethyl, andpropyl radicals which combine either with the hydroxyl radicals to formmethanol, ethanol, and propanol, or with the hydrogen radicals to formmethane, ethane, and propane.

The methanol produced by the operation of the distillation unit 72 isrecovered at outlet 96. A pressure swing absorber 97 receives naturalgas and hydrogen from the distillation unit 72. Unreacted natural gas isrecovered from the pressure swing absorber 97 at outlet 98 and isreturned to the distillation unit 72 through piping 88. Byproducthydrogen produced in the distillation unit 72 is recovered at outlet 100and is directed to a fuel cell 102.

Within the fuel cell 102, hydrogen recovered from the distillation unit72 is combined with oxygen from the atmosphere to produce electricitywhich is recovered at terminal 104 and water which is recovered atoutlet 106 and returned to the distillation unit 72 through piping 108.As will be appreciated by those skilled in the art, a conventionalengine/generator may be used in lieu of the fuel cell 102; however, theuse of a fuel cell is preferred due to its greater efficiency.

The use of the hydrogen recovered from the distillation unit 72 toproduce electricity comprises an important advantage in the use of thepresent invention in that the electricity thus produced may be utilizedto provide artificial lighting in those instances in which the apparatus70 is situated at a remote location and/or to provide heating for thedistillation unit 72. As is shown in FIG. 4, electricity from the fuelcell 102 may also be used to operate the radiation sources and 76 themotor 84.

In addition to producing methanol, the apparatus 70 converts otheralkanes present in the natural gas to their respective alcohols, namely:ethanol, normal propanol, and isopropanol. The higher alcohols thusproduced are recovered from the distillation 72 at outlet 110 and aredirected to a reverse osmosis unit 112, and from the reverse osmosisunit 112 to a secondary distillation unit 114 to produce purer forms ofthe higher alcohols. Like the distillation unit 72, the distillationunit 114 is provided with a heat source adequate to effect the desireddistillation. Unrecovered materials from the secondary distillation unit114 are returned to the reverse osmosis unit 112 through piping 116. Thereverse osmosis unit 112 also produces water which is returned to thedistillation unit 72 through the piping 108.

Typically, the water which is returned to the distillation unit 72 fromthe fuel cell 102 and the reverse osmosis unit 112 is sufficient tomaintain a predetermined quantity of water therein. The distillationunit 72 is initially filled from a water supply 118 which is alsoavailable to supplement the water received from the fuel cell 102 andthe reverse osmosis unit 112 if necessary to maintain an adequate supplyof water in the distillation unit 72.

In lieu of the motor 84, the disk 78 may be oscillated using a torsionmotor or reciprocated using a motor and crank assembly. Other apparatusfor effecting relative movement between the partition 80 and the water74 will suggest themselves to those skilled in the art.

As will be appreciated by those skilled in the art, it is known toproduce gas permeable partitions entirely from photocatalytic material,including titanium-based catalytic materials. FIG. 6 illustrates ahollow disk 78 having a gas permeable partition 120 formed entirely fromone or more catalytic materials. Such construction eliminates the needof forming a catalytic layer on the surface of a gas permeablepartition.

Those skilled in the art will appreciate the fact that the method andapparatus of the present invention can be utilized to convert gasesother than methane and natural gas into valuable products. For example,the method and apparatus of the present invention can be utilized toconvert carbon dioxide to methanol and methane. The adaptation of otherchemical processes to the method and apparatus of the present inventionwill readily suggest themselves to those skilled in the art.

Referring to FIGS. 7 and 8, there is shown a hollow disk assembly 130comprising a fifth embodiment of the invention. The hollow disk assembly130 includes a hollow disk 132 which is supported on a hollow tube 134for rotation, oscillation, or reciprocation relative to a quantity ofwater (not shown in FIGS. 7 and 8). The hollow disk assembly 130 furtherincludes a porous partition 136 supported on the hollow disk 132 and alayer or plate of catalyst material 138 supported on the porouspartition 136.

The hollow disk assembly 130 comprising the fifth embodiment of theinvention differs from the hollow disk assembly of FIG. 4 in twosignificant aspects. First, the hollow disk 132 is provided with amirrored surface 140 formed on the interior surface of the hollow disk132 opposite the porous partition 136. Thus, the mirrored surface 140functions to reflect electromagnetic radiation passing through thecatalytic material 138 and the porous partition 136 back to thecatalytic material 138, thereby substantially increasing the efficiencyof the interaction between the electromagnetic radiation and thecatalytic material 138.

Additionally, the porous plate 136 includes a quantity of a fluorescentmaterial. The fluorescent material which is included in the porouspartition 136 is selected to respond to broad-band electromagneticradiation to produce an output comprising narrow band electromagneticradiation which is specifically matched to the band width of theradiation which activates the catalytic material 138. In this manner,the efficiency of the catalytic reaction is substantially increasedbecause the portion of the electromagnetic radiation which wouldotherwise be unused is transformed by the fluorescent material intoradiation within the band width comprising the input requirements of thecatalytic material.

Referring to FIGS. 9 and 10, there is shown a hollow disk assembly 150comprising a sixth embodiment of the invention. The hollow disk assembly150 includes a hollow disk 152 which is supported on a hollow tube 154for rotation, oscillation, or reciprocation relative to a quantity ofwater (not shown in FIGS. 9 and 10). The hollow disk assembly 150further includes a porous partition 156 supported on the hollow disk 152and a layer or plate of catalyst material 158 supported on the porouspartition 156.

The hollow disk assembly 150 comprising the sixth embodiment of theinvention differs from the hollow disk assembly of FIG. 4 in twosignificant aspects. First, the hollow disk 152 is provided with amirrored surface 160 formed on the interior surface of the hollow disk152 opposite the porous partition 156. Thus, the mirrored surface 160functions to reflect electromagnetic radiation passing through thecatalytic layer 158 and the porous partition 156 back to the catalyticlayer 156, thereby substantially increasing the efficiency of theinteraction between the electromagnetic radiation and the catalyticlayer.

Additionally, the catalyst material 158 includes a quantity of aflourescent material. The flourescent material which is included in thecatalyst material 158 is selected to respond to broad-bandelectromagnetic radiation to produce an output comprising narrow bandelectromagnetic radiation which is specifically matched to the bandwidth of the radiation which activates the catalytic material 158. Inthis manner, the efficiency of the catalytic reaction is substantiallyincreased because the portion of the electromagnetic radiation whichwould otherwise be unused is transformed by the flourescent materialinto radiation within the band width comprising the input requirementsof the catalytic layer.

Referring to FIGS. 11 and 12, there is shown a hollow disk assembly 170comprising a seventh embodiment of the invention. The hollow diskassembly 170 includes a hollow disk 172 which is supported on a hollowtube 174 for rotation, oscillation, or reciprocation relative to aquantity of water (not shown in FIGS. 11 and 12). The hollow diskassembly 170 further includes a porous partition 176 supported on thehollow disk 172 and a layer or plate of catalyst material 178 supportedon the porous partition 176.

The hollow disk assembly 170 comprising the seventh embodiment of theinvention differs from the hollow disk assembly of FIG. 4 in twosignificant aspects. First, the hollow disk 172 is provided with amirrored surface 180 formed on the interior surface of the hollow disk172 opposite the porous partition 176. Thus, the mirrored surface 180functions to reflect electromagnetic radiation passing through thecatalytic layer 178 and the porous partition 176 back to the catalyticlayer 176, thereby substantially increasing the efficiency of theinteraction between the electromagnetic radiation and the catalyticlayer.

Second, in addition to the porous plate 176 and the layer or plate ofcatalyst material 178, the seventh embodiment includes a plate 182comprising a flourescent material. The flourescent material which isincluded in the plate 182 is selected to respond to broad-bandelectromagnetic radiation to produce an output comprising narrow bandelectromagnetic radiation which is specifically matched to the bandwidth of the radiation which activates the catalytic material 178. Inthis manner, the efficiency of the catalytic reaction is substantiallyincreased because the portion of the electromagnetic radiation whichwould otherwise be unused is transformed by the flourescent materialinto radiation within the band width comprising the input requirementsof the catalytic layer.

In FIGS. 13 and 14 there is shown a hollow disk assembly 190 comprisingan eighth embodiment of the invention. The hollow disk assembly 190includes a hollow disk 192 which is supported on a hollow tube 194 forrotation, oscillation, or reciprocation relative to a quantity of water(not shown in FIGS. 13 and 14). A porous partition 196 is supported onthe hollow disk 192 and in turn supports a plate or layer of catalyticmaterial 198.

The hollow disk assembly 190 differs from the hollow disk assemblies130, 150, and 170 in that rather than employing a mirrored surfaceformed directly on the hollow disk 192, there is provided a separatereflective disk 199. The reflective disk 199 may be fabricated fromglass or transparent plastic, in which case the interior surface thereofis provided with a reflective layer in the manner of a conventionalmirror. Alternatively, the reflective disk 199 may comprise stainlesssteel or other metal having a highly polished exterior surface.

Those skilled in the art will appreciate the fact that a mirroredsurface formed on an appropriate interior surface may be used in any ofthe embodiments of the invention illustrated in FIGS. 1 through 12,inclusive, and described hereinabove in conjunction therewith. Likewise,a separate mirrored member or members having a variety of geometricconfigurations can be used in conjunction with any of the embodiments ofthe invention illustrated in FIGS. 1 through 12, inclusive, anddescribed hereinabove in conjunction therewith. Likewise, any of theflourescent material constructions illustrated in FIGS. 7 through 12,inclusive, and described hereinabove in conjunction therewith can beutilized in conjunction with any of the embodiments of the inventionillustrated in FIGS. 1 through 6, inclusive, 13 and 14 and describedhereinabove in conjunction therewith.

Referring to FIG. 15, there is shown a method of and apparatus formanufacturing methanol from methane or natural gas 200 comprising aninth embodiment of the invention. In accordance with a ninthembodiment, a plurality of porous partitions 202 are mounted in apredetermined array which may be either linear, circular,three-dimensional, etc. The porous partition 102 may be tubular inshape, however, any desired geometrical configuration may be utilized inthe construction of the porous partitions 102 depending upon therequirements of particular applications of the invention. Each of theporous partitions 202 has a photocatalytic layer formed on its exteriorsurface.

A partition 204 which is transparent to electromagnetic radiation ispositioned on each side of each porous partition 202. Within eachtransparent partition 204 there is provided a source of electromagneticradiation 206 which may comprise, for example, a source of ultravioletlight, it being understood that other sources of electromagneticradiation providing the same or different types of radiation may beutilized in the practice of the invention depending upon therequirements of particular applications thereof.

Methane or natural gas received from a source 208 is directed into theinterior of each porous partition 202 from a first manifold 210.Simultaneously, water received from a source 212 is directed through asecond manifold 214 into the spaces between the porous partitions 202and the electromagnetic radiation transparent partitions 204. Withineach porous partition 202 the pressure of the methane or natural gas ismaintained just high enough to cause methane or natural gas to flowoutwardly through the porous partition while preventing the flow ofwater inwardly through the porous partition.

In the operation of the apparatus 200, relative movement is continuouslyeffected between the water and the exterior surfaces of the porouspartitions 202 using, for example, the techniques shown in FIGS. 1, 2,and 3 and described hereinabove in conjunction therewith.Electromagnetic radiation from the sources 206 activates the catalyticlayers on the exterior surfaces of the porous partitions 202 to formhydroxyl radicals from the water. The hydroxyl radicals combine with themethane to form methanol, and if natural gas is used in the operation ofthe apparatus 200, to form methanol and higher alcohols. The energy fromthe electromagnetic radiation sources 206 is sufficient to distill themethanol, and, if present, the higher alcohols from the water forrecovery at an outlet 216. The remaining water is recovered at an outlet218 and is returned to the manifold 214 for reuse.

A method of manufacturing methanol and higher alcohols from natural gasis shown in the flow chart comprising FIG. 16 which depicts a tenthembodiment of the invention. In accordance with the tenth embodiment,natural gas or methane is mixed with an oxidizer such as oxygen,peroxide, etc. in accordance with a predetermined ratio. The mixturecomprising natural gas or methane and an oxidizer is then directedthrough a porous partition having a photocatalytic exterior surface. Thephotocatalytic exterior surface is surrounded by a quantity of water,and relative movement is continuously maintained between thephotocatalytic surface and the water. Electromagnetic energy is directedonto the photocatalytic layer which forms hydroxyl radicals from thewater. The hydroxyl radicals combine with methyl radicals from themethane to form methanol. If natural gas is used, the hydroxyl radicalscombine with methyl, ethyl, and propyl radicals to form methanol andhigher alcohols. The alcohol(s) thus produced are recovered along withbyproduct hydrogen. The presence of the oxidizer in the mixture causesthe reaction to be self-sustaining.

Although preferred embodiments of the invention have been illustrated inthe accompanying Drawing and described in the foregoing DetailedDescription, it will be understood that the invention is not limited tothe embodiments disclosed but is capable of numerous rearrangements,modifications, and substitutions of parts and elements without departingfrom the spirit of the invention.

We claim:
 1. A method of manufacturing methanol and higher alcohols fromnatural gas comprising the steps of: providing a hollow chamber having agas permeable partition; providing a quantity of light activatedcatalytic material comprising at least the exterior of the gas permeablepartition; directing electromagnetic radiation onto the catalyticmaterial, at least a portion of the electromagnetic radiation passingthrough the catalytic material and the gas permeable partition into thehollow chamber; and reflecting electromagnetic radiation passing throughthe porous partition back through the gas permeable partition and intoengagement with the catalytic material.
 2. The method of claim 1 furtherincluding the step of providing a reflective surface formed directly onpart of the hollow chamber.
 3. The method of claim 1 further includingthe step of providing a separate reflective member positioned within thehollow chamber.
 4. The method of claim 1 further characterized by:providing catalytic material characterized by a predetermined activationband width; directing electromagnetic radiation having a band widthencompassing but wider than the activation band width of the catalyticmaterial onto the catalytic material; providing a quantity offluorescent material responsive to electromagnetic radiation forproducing an output radiation having a band width at least partiallywithin the activation band of the catalytic material; and directing theoutput radiation from the fluorescent material into engagement with thecatalytic material.
 5. The method of claim 4 further including the stepof incorporating the fluorescent material into the gas permeablepartition of the hollow chamber.
 6. The method of claim 4 furtherincluding the steps of: providing a layer of catalytic material separatefrom the gas permeable partition; and incorporating the fluorescentmaterial into the catalytic material.
 7. The method of claim 4 furtherincluding the steps of: providing a layer of catalytic material separatefrom the gas permeable partition; providing a layer of fluorescentmaterial separate from the layer of catalytic material and the gaspermeable partition; and positioning the layer of fluorescent materialbetween the layer of catalytic material and the gas permeable partition.8. A method of manufacturing methanol and higher alcohols from naturalgas comprising the steps of: providing a hollow chamber including a gaspermeable partition; providing a quantity of light-activated catalyticmaterial having a predetermined activation band width comprising atleast the exterior of the gas permeable partition; directingelectromagnetic radiation having a predetermined band width wider thanand encompassing the activation band width of the catalytic materialonto the catalytic material; providing a quantity of fluorescentmaterial responsive to the electromagnetic radiation from the source forproducing output radiation having a band width at least partially withinthe activation band width of the catalytic material; and directing theoutput radiation from the fluorescent material into engagement with thecatalytic material.
 9. The method of claim 8 further including the stepsof incorporating the fluorescent material into the gas permeablepartition of the hollow chamber.
 10. The method of claim 8 including theadditional steps of providing a layer of catalytic material separatefrom the gas permeable partition and incorporating the fluorescentmaterial into the layer of catalytic material.
 11. The method of claim 8wherein at least part of the electromagnetic radiation from the sourcepasses through the catalytic material and the gas permeable partitioninto the hollow chamber and including the additional step of providingthe reflective surface within the hollow chamber for reflectingelectromagnetic radiation passing through the gas permeable partitionback through the gas permeable partition and into engagement with thefluorescent material and the catalytic material.
 12. The method of claim11 including the additional step of forming the reflective surface onpart of the hollow chamber.
 13. The improvement according to claim 12including additional steps for providing a separate member positionedwithin the hollow chamber.
 14. A method for manufacturing methanol andhigher alcohols from natural gas including the steps of: providing ahollow chamber including a gas permeable partition; providing a quantityof light-activated catalytic material having a predetermined activationband width comprising at least the exterior of the gas permeablepartition; directing electromagnetic radiation having a predeterminedband width encompassing the activation band width of the catalyticmaterial onto the catalytic material, at least a portion of theelectromagnetic radiation passing through the catalytic material and thegas permeable partition into the hollow chamber; providing the quantityof fluorescent material responsive to said electromagnetic radiationfrom the source for producing output radiation having a band width atleast partially within the activation band width of the catalyticmaterial; directing the output radiation from the fluorescent materialinto engagement with the catalytic material; and providing a reflectivesurface within the hollow chamber for reflecting electromagneticradiation passing through the gas permeable partition back through thegas permeable partition and into engagement with the catalytic materialand the flourescent material.